Method of forming nuclear alkyl derivatives of phenols



METHOD or some woman psmva'rrvss or reasons 7 Lawre ce-n. Elett,Hamburg, N. 1., assignor to National Anilihe dt Chemical Company, Inc.,New'York, N. 1, a corporation of New York No Drawing. ApplicationSeptember 28, 1935, Se-

rial No. 42.354. lbenewed December 1, 1936 15 Retest-s24 nate'dderivatives thereof useful as detergents.

filkyl phenol sulfonates having the general form a:

in which A represents hydrogen or a methyl a group, R represents an openchain alkyl hydrocarbon (saturated or unsaturated) containing 12 a ormore (preferably 12 to 23', and especially 14 to 19) carbon atoms, and Mrepresents hydrogen or a metal, particulary an alkali metal, or anammonium or organic ammonium radical, constitute an important class ofsynthetic detergent materials.

One important method of preparing them involves condensing phenol(hydroxybenzene) or a cresol (1,2-, 1,3- or 1,4-methylhydroxybenzene)withan alkyl halide containing atJeast 12' carbon atoms, moreparticularly 1; to 23 carbon' is preferably atomsjand especially 14'to19 carbon atoms, and sulfonating the resulting alkyl phenol or cresol.According to the present invention, the 'condnsation of phenol or acresol with an alkyl halide containingat least 12 carbon atoms, moreparticulary 12ftq23 carbon atoms, and especially 14 to 19 carbon "atoms,is carried out by heating phenol or a cresol with the alkyl halide and'azinc condensing agent at a condensation temperature for a considerableperiod of time after substan-i tially no increase in yield ofcondensation product results from further heating at said temperature.

As zinc condensing agents there may be em- 'ployed anhydrous zincchloride and/or a zinc substance capable of reactingwith a hydrohalidetoform a zinc halide (as for example, zinc oxide, 'zincjetc.) During thecondensation with zinc or' zinc'oxide, a zinc halide is probably formedand hence also with these substances the condensetion apparently takesplace in the presence of a zinc halide.- In

--- r as the condensingagent general, anhydrous zinc chloride since, thewhole, it gives more uniform products and better yields, as well assulfonated products of siiperior color and quality. It is noted thatzinc chloride referred to as anhydrousmay contain small amounts ofwater,for instance, such as are absorbed from the surrounding atmosphereor otherwise in commercial operation, but in'suiiicient to interferewith its action as a condensing agent. Even when the zinc chloridecontains an equal'weight of water it functions as a condensing agent;but such large amounts of water arepreferably avoided.

- The proportion of alkyl halide employed with I respect to thephenolmay vary; but preferably the amount employed is such that not more thanone and! radical of the type represented by R'in the foregoing formulais contained in the resulting alkyl phenol. Thus, at least 1.25 mols of.phenol per mol of alkyl halide is preferably em-- Dloyed in thecondensation. A molar ratio as low as 1 to 1, or even lower, may beemployed,

but the yield of'the resulting alkyl phenol con- .tainingone alkylradical of the said type represented by R will be less.

The amount of zinc chloride or other zinc substance employed is only afraction of the weight of the alkyl halide and may be as low as 1 percent of the weight of the alkyl halide. In general an amount of zincchloride equal to about 5 to about 20 per cent of the weight of thealkyl halide is preferably employed althoughgreater amounts may be used.5' While thecondensation may be carried out at 1 various temperatures,as for example from room temperature to -refluxing (about 190 C.) orhigher, it has been found according to the present invention thattemperatures above 100 C. are preferably employed with zinc condensingagents.

The action of the 'alkyl halide and the phenol. or cresol may be carriedout may be varied; however, the minimum period of heating of thereaction mixture at a condensation temperature is considerably in excessof that required to effect mere combination of the phenol compound andthe alkyl halide. phenols resulting from the extended heating inaccordance with the present invention, when con-.-

verted to alkyl phenol sulfonates, result in products of much superiordetergent action as compared with those produced by heating at the sametemperature merely until condensation appears to be complete, asindicated by the yield of condensation product. '1h1.1s,-inthe'condensation of tetradecyl chloride and phenol with-the aid of timeduring which the condensation re-' I have found that the alkyl 'thatresulting from carrying out the reaction at anhydrous zinc chloride,heating the reaction mixture for 1 hour at 135 C. results in a yield oicondensation products substantially equal to higher temperatures and/orfor considerably longer periods of time. The detergent action of theresulting product, when converted to a detergent by suli'onation of thealkyl phenol, is very much inferior to of a product resulting fromheating the reaction mixture for more than 4 hours at-135 0. Hence, inaccordance with the 1 present invention, at temperatures of about 135ture may be extended to 16 hours or more without seriously harming thequality or decreasing the Y eld of the alkyl phenol.

Without limiting the invention to any theo retical considerations itappears the continued heating probably results in rearrangement to thecorresponding alkyl. phenols of phenol others which may be formed, andprobably also converts objectionable impuritiu to other products whichdo'not. appear in the alkyl phenol sulfonate produ ts when the alkylphenols are converted to deents by sulfonation, or if present in saidsulfonation products, do not exert a deleterious iniiuence.

The invention will be illustrated by the follow ing specific examples inwhich the parts are by weight and thetemperatures are'in degreescentigrade. It will be understood by those skilled in the art that thescope of theinvention'is not limited to these specific examples.

Exams l.-Sodium cetul phenol sullonote A mixture or parts of 'cetylchloride (prepared i'rom commercial cetyl alcoholand boiling within therange 160 to 210 at 5 mm. pressure) 80 parts of phenol and 10 parts ofanhydrous zinc chloride,flwhile being agitated vigorously, is heated toa temperature of 175 and then is maintained for 6 hours at a temperatureof 175 to 185. The reaction mixture is allowed to cool, and the oil 'isdecanted oil and fractionally distilled in a vacuum. The fraction of thedistillate boiling from 190 to 250 at 5 mm. 01 mercury pressure isseparately collected. The product, which comprises cetyl phenol, is aviscous oil which is partially-solid at room temperature and completelysolid at 5'. An equal weight of sulfuric acid is added to the product ata temperature of 10" to 25. The reaction massis agitated whilemaintaining this temperature until a test portion is not turbid indilute alkaline solution. After drowning in ice water the solution isneutralized with aqueous sodium hydroxide andevaporated to dryness.

Exluun 2.--Sodium mvristyl para-cresol sulfonate a mixture 01 parts ofmyristyl bromide -(prepared from the alcohol and boiling within therange to 170 at 8 mm. pressure), 102

A parts of para-cresol-- and IO'parts of zinc chlo- *ridefli'as acondensing agent) is agitated and heated at a temperature of about 175(:59) for 18 hours. Aiter cooling, myristyl-para-cresol is obtained fromthe mass by decantation, fractional distillation in a vacuum, andcollection of the fraction boiling from 175 to 285' at a prusure of 5mm. of mercury. The product is a' light-brown viscous oil. An equalweight of 100% sulfuric acid is added to the product at a temperature of10 to 25..= The reaction mass -is agitated while maintaining thistemperature until a test portion is not turbid in dilute alkalinesolution; After drowning in ice water the solution is neutralized withaqueous sodium hydroxide and evaporated to dryness.

Exlunn: 3.-Sodium laurel phenol .ndlonate Amixture of 185 parts oflauryl chloride (prepared from commercial lauryl alcohol), 100 parts ofphenol and 30 parts of zinc chloride (as a condensing agent) is heatedwith agitation at a temperture of 170 to 180 under a renux condenser for20 hours. The reaction mixture is allowed to cool and the oil whichseparates is decanted oil and fractionally distilled in a vac,-

uum. The fraction of the distillate boiling between 150 and 230' at 4mm. pressure of mercury is separately collected. It of lauryl phenol inadmixture with other aliyl phenols. To 20 parts oi the lauryl phenolproduct thus obtained, there is slowly added with agitation 20 parts ofsulfuric acid monohydrate, and the mixture is maintained at atemperature of 30 to 35 for 3 hours or. until the desiredsulfonationiseflected. Themassisdilutedwith400,

parts of water, and the solution thus obtained is neutralized withcaustic soda and evaporated to dryness. The product thus obtainedcomprises a mixture of alkyl phenol sulfoniites together with somesodium sulfate, of which a predominant compound is the [sodium salt oflauryl phenol sulfonate having the probable formula:

, Gia a I CHI 8 O Na Ensues-chlorine is passed into 328 parts of akerosene (a Pennsylvania petroleum distillate) which boils from 235 to240 at 750 mm. pressure while maintaining the temperature at 50. Tofacilitate the reaction, the reaction mixture, which is contained in aglass reaction vessel, is subjected. to direct sunlight during thetreatment with chlorine and is well agitated. When the weight of thereaction mixture has increased about 58 parts the introductionofchlorine is discontinued and the agitation continued for about anadditional fifteen minutes.

The reaction mixture is subjected to fractional distillation and amiddle fraction is collected'between and 175 at 34 mm, It comprisesmainly monochlorinated hydrocarbons.-

150 parts of the resulting chlorinated hydrocarbon product, 150 parts ofphenol and 130 parts ofanhydrous zinc chloride are agitated while beingheated at in a vessel provided with areilux condenser. After about nvehours the heating is discontinued, the mixture is allowed tocool, iswashed with dilute'hydrochloric acid (100 parts of 10 per cent. HCl) andis then distilled at 4 mm. pressure. The portion of the product boil-'ing from 140 to 250 at 4 mm. pressure is separately collected, aboutthree-fourths ofwhichboils between and 220. The is computed arca esmainly of a mixture of l phenols which may be represented by the generalformula:

in which R isa primary, secondary or tertiary alkyl group, which for themost part is probably in the para-position to the hydroxy group, theaverage number of carbon atoms in the groups represented by R probablybeing about 14.

To 25 parts of the resultingalkyl phenol mix,- ture there is slowlyadded with good agitation 81 parts of per cent sulfuric acid. The acidis added at such a rate that the final temperature of the mixture, asthe resultof the heat of reaction, is about 60". After allot thesulfuric acidhas been added, the mixture is wed to 80 and held there forabout 15'to 20 minutes to complete the sulionation. drowned in 200 partsof water, and caustic soda is added until the resulting solution isslightly.

alkaline to Brom Cresol GreenPaper. The faintly alkaline mass is thenevaporated to dryness, or it is converted to a dry product in any othersuitable manner. The resulting product comprises a mixture of thesodiumsalts of sulionated I phenols, in which the allsyl groups have anaverage content of about is carbon atoms, mixed with the sodium sulfateresulting from heat -=-.v tion of the residual sulfuric acid, and otherimpuri= ties. It is a powdery mass of the nature of a soap powder, andis readily soluble in water, also in neutral, acid and weakly alkalineaqueous solutlons.

EXAMPLE 5.Chlorlne is passed into e00 parts of a kerosene boiling fromabout 195 to about 300 (and boiling for the most part from about 225 to275) and having a specific gravity of 0.799 at 24. Thelrerose'ne iscontained in a lead lined vessel and is maintained at 50. Thechlorination is continued until the reaction ure reaches a specificgravity of 0.01. 200-parts oi the resulting chlorinated mixture, partsoi phenol and 25 parts of zinc dust are heated under refluxing, andagitation at 170 for about a hours. The oily product is decanted fromthe mic residues and fractionaily distilled in a vacuum. The

, portion of the distillate boiling from 160 to 250 at 4 mm. pressure isseparately collected. it comprises a mixture of alkyl phenols in whichthe alkyl groups have a probable average content oi 13 carbon atoms.When sulfonated it produces a detergent.

EXAMPLE 8.-hlorine is passed into is here (a purified Pennsylvaniapetroleum distillate) boiling from 2&5 to 315, and of which 90 per 5tion. The chlorination is carried out in the dark, but to facilitate thechlorination the kerosene 560 parts of the resulting :1

The" reaction mass is then nated hydrocarbons, 350 parts of phenol and28 parts of granular anhydrous zinc chloride are agitated at roomtemperature for about 30 hours and then heated, with agitation, at aboutfor about 5 hours. The resulting reaction mass is cooled and added toabout 600 parts of water, the mixture is heated to 70 with agitation,8.1-. lowed to settle, and the upper, oil. layer is separated and washedwith hot water to remove zinc chloride and residual phenol. The washedoil is then treated with a small amount of alkali (7 parts of a 50 percent solution of sodium hydroxide) and-distilled in vacuo (e. g., 4 mm.pressure) in a still equipped with a fractionating. column.

Fractions boiling between about and 230 at 4 mm. pressure are collectedas separate products or as one product.

4 262 parts oi one of the resulting mixtures oi alkyl phenols (theresulting product or one oi the fractions thereof) are sulfonated byagitating well with 262 parts of 100 per cent sulfuric acid, whilemaintaining the temperature at 20? to 30. When the sulionation has beeneffected, the reaction mass is drowned in 1500 parts oi! water,

, invention.

Thus, phenol, ortho-, meta-, o'r para-cresol or their mixtures may beemployed.

Various alkyl halides containing at least 12 carbon atoms may beemployed; as for example, chlorides and bromides of the saturated andunsaturated hydrocarbons of the aliphatic class, includingstraight-chain and branched-chain carbon linkages, in which the halogenatom is linked to an end carbon atom or an intermediate car bon atom,and particularly the monochlorides and monobromides. Those in which thehydrocarbon radical of thehalide contains a branched carbon chain orwhich result in a product in which the radical represented by R in theforc going formula contains a branched carbon chain are preferred.Further, mixed'alkyl halides are preferred'and particularly mixtures ofchlorinated hydrocarbon mixtures such as can be obtained by thechlorination or hromination of selected fractions of mineral oil orrelated hydrocarbon mixtures, containing predominantly at least 12carbon atoms, and preferably an average of about 14 to 19 carbon atoms.

When the alkyl phenol sulfonates are to be em ployed as detergents, thecrude alkyl phenol resulting from the condensation of the alkyl halidewith phenol or a cresol is preferably purified-as for example, byfractional vacuum distillation,

and the purified compound is preferably employed for sulfonation. In thefractional distillation, a pressure not exceeding 30 mm., andparticularly not exceeding 10 mm., is preferred. Preferably the purifiedalkyl phenol is collected as a middle fraction of the distillate over 'atemperature range which may be as high as 140 C., but which preferablydoes not exceed 100 0.

As sulfonating agents there may be employed sulfuric acids of variousstrengths (e. g., 66 B. sulfuric acid, sulfuric acid monohydrate, oleum)chlorsulfonic acid, etc.

The sulionationmay be carried out in the presarms or ace at an inertorsanlcsolvent or diluent and in the presence or absence of a'wifenation assistant. As solvents or diluent theremay be employed anyinert organic liquid which is not readily sulfonated, such ashalogenated hydrocarbons of the aliphatic and aromatic se ries; as forexample, carbon tetrachloride, di-.

chlorethane, tetrachlorethane, dichlorbenzene, etc. As suli'onationassistants there may be em-' ployed the lower organic acids and/or their.anhydrides, as for example, acetic acid, acetic-anhydride, etc. I

The temperature at which the sulfonation is carried out may vary withinwide limits. For example, temperatures as low as about and as high asabout 140 may be employed. In general the more vigorous the sulfonatingagent the lower is the preferred temperature. Ordinarily the completionof the sulfonation is carried out at a temperature in the neighborhoodof about 35' to about 80 0. The ratio of sulfonating agent employed withrespect to the alkyl phenol also may be varied. Thus an amountof-suliuric acid or other sulfonating agent equivalent to from 1 toabout 5 parts by weight of sulfuric acid monohydrate per part by weightof thealkyl phenol may be employed.

The extent to which the sulfonation is carried out may vary with theindividual material being sulfonated and the use to be made of the mito-"nated product. In general the extent of sulfonation of the alkyl phenoltreated is such as to form chiefly the monosulionic acid of thealkylphenol, and to sulfonate impurities as well, it

. present.

The alkyl phenol sulfonates may be recovered in the form of their freesulfonic acids or in the form of salts of metals (as for example, of thealkali metals) or of organic bases, or of ammonia, etc. The salts may beobtained in any suitable manner, for example by reacting the sulfonatedproduct, either in the crude form resulting from the sulfonation or in apurified form, witha metal oxide orhydroxide, ammonia or an organicbase, or of a suitable salt of one of these, in an amount adapted toform a neutral product.

in said reaction mixtures, which mixtures of salts are also useful assuch. Thus, the sulfonation reaction mixture resulting from-thetreatment of the alkyl phenol or 'cresol with an amount of sulfonatingagent in excess of that theoretically required to effect the desireddegree of sulfonation may be treated with a suitable inorganicor organlcbase or basic salt (as for example, one of,

those mentioned) and .the resulting mixture of ithe salt of thesulfonated alkyl phenol or cresol and the organic or inorganic salt (asfor example, sodium sulfate) may be jointly isolated from the reactionmixture and employed as such. If it is desired to produce a salt of thesulfonated albi phenol or cresol in a form substantially free product isobtained.

from metal salts of inorganic acids (for example,

rivatives of phenolswhich comprises heating at a. condensationtemperature a reaction mixture containing a phenol compound selectedfrom the group consisting of phenol and its mono-methyl derivatives, anopen-chain allryl mono-halide containing at least 12 carbon atoms and azinc condensing agent, and continuing the heating for a considerableperiod of time after substan-.

tially no increase in yield of condensation product is obtained.

2. The method of producing nuclear alkyl derivatives'of phenols, whichcomprises heating-at .a condensation temperature a reaction mixturecontaining a phenol compound selected from the group consisting ofphenol and its mono-methyl derivatives, an open-chain alk'ylmono-chloride containing 12 to 23 carbon atoms and a zinc condensingagent, and continuing the heating for a considerable period of timeafter substantially no increase in yield of condensation product isobtained.

3.,The method of producing nuclear alkyl derivatives of phenols whichcomprises heating a reaction mixture containing a phenol compoundselected from the group consisting of phenol and its mono-methylderivatives, an open-chain alkyl mono-halide containing at least 12carbon atoms and a zinc condensing agent at a temperatureof at least 1000., and continuing the heating for.

a considerable period of time after substantially no increase in yieldof condensation product is obtained, I

4. The method of producing nuclear alkyl derivatives of phenols, whichcomprises heating at a condensation temperature a reaction mixturecontaining a phenol compound selected from the group consisting ofphenol and its mono-methyl derivatives, an open-chain alkyl mono-halidecontaining at least 12 carbon atoms and zinc chloride as a condensingagent, and continuing the heating for aconsiderable period of time aftersubstantially no increase in yield of condensation 5. The method ofproducing nuclear'alkyl derivatives of phenols, which comprises heatingat a condensation temperature a reaction mixture containing a phenolcompound selected from the group consisting of .phenol and itsmonomethyl derivatives, an open -chain alkyl monohalide containing atleast12 carbon atoms, and zinc chloride as a condensing agent, andcontinuing the heating for a considerable period of time aftersubstantiallyno increase in yield of-' condensation product is obtained,the amount of 7 zinc chloride being not more than 20% of the weight ofthe alkyl mono-halide.

6. The'method of producing nuclear alkyl de-" rivatives of phenol, whichcomprises heating at a condensation temperature a reaction mixturecontaining phenol, an open-chain alkyl monohalide containing at least12' carbon atoms, and a zinc condensing agent, the amount of phenolbeing at least 1.25 mol per mol of the alkyl halide,

v and continuing the heating for a considerable n period of time aftersubstantially no incre in yield of condensation product is obtained.

'1. The method of producing nuclear alhyi derivatives of phenol, whichcomprises hea at a condensation temperature a reaction mixturecontaining phenol, an open-chain alkyl monochloride containing 12 to 23carbon atoms, and a zinc condensing agent, the amount of phenol being atleast 1.25 moi per mol of the alkyl chicride, and continuing the heatingfor a considerable period of time after substantially no increase inyield of condensation product is obtained.

8. The method of producing nuclear allwl derivatives of phenol whichcomprises heating a reaction mixture containing phenol, an open-chainalkyl mono-chloride containing at least 12 carbon atoms, and a zinccondensing agent at a temperature of at least 100 C.,.the amount ofphenol being at least 1.25 mol per mol of the alkyl chloride, andcontinuing theheating for a considerable period of timeaftersubstantially no incree in yield of condensation product is obtained.

9. The method of producing nuclear alhyl de= rivativesof phenols whichcomprisesheating a reaction mixture containing a phenol compoundselected from the group'consisting of phenol and its mono-methylderivatives, an open-chain alhyl mono-halide containing at least 12carbon atoms. and a zinccondensing agent at a temperature of at least135 C. for at least a hours.

10. The method of producing nuclear all derivatives of phenols whichcomprises heating areaction mixture containing a phenol compoundselected from the group consisting of phenol and its mono-ethylderivatives, an open-c m; alkyl mono-chloride containing 12 to 23 carbonatoms,-

Patent rs;, 3 1 66 1 6 cnarrrrcarsf or-conascrrom1 marshes a, re.

It is hereby certified that error appears. 'the'printedspecification 12.The ar od of producing nuclear alkyl derivatives of phenols whichcomprises heating a reaction mixture containing a phenol compoundselected from the group consisting of phenol and its mono-methylderivatives, an open-chain alkyl mono-chloride containing12 to 23 carbonatoms, and zinc chloride as a condensing agent, at a temperature of atleast 160 C. for at least i.

I ing for a considerable period of time after substantially no increasein yield vof condensation '2 rivatives of phenols useful as detergents,which comprises heating a reaction mixture containing a phenol compoundselected from the group consisting of phenol and its mono-methylderivatives,

an open-chain alkyl mono-halide containing at least 12 carbon atoms, anda zinc condensing agent at a temperature of at least 135 C. for at 3 ofthe above numbered patent requiring QOI'I'QCtiZIfidfOIlOWB: Page 5,secto the record of the case in t e Patent Office; i

Signed and sealed this 29th day of August,- A. D. 1959.

(Seal) I Leslie Frazer, I Acting (loimnisaionor of Patents.

1ine3, for "30' hours" read 5 neural and that thesaid Letters Patentshouldbe read with. this correction therein that the same naiyconformi

